High-performance adsorbents based on activated carbon having high meso- and macropososity

ABSTRACT

The invention concerns high-performance adsorbents based on activated carbon of high meso- and macroporosity which are present in the form of discrete grains of activated carbon, wherein
         at least 55% of the total pore volume of the high-performance adsorbents are formed by pores (i.e. meso- and macropores) having pore diameters of more than 20 Å,   the high-performance adsorbents have a measure of central tendency pore diameter of more than 25 Å, and   the high-performance adsorbents have a BET surface area of at least 1250 m 2 /g.       

     These high-performance adsorbents are obtainable by a novel process comprising specific two-stage activation, and have, in addition to the aforementioned properties, an excellent abrasion and bursting resistance, so that they are useful for a multiplicity of different applications.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a National Stage filing of International ApplicationPCT/EP2008/000606, filed Jan. 25, 2008, claiming priority to GermanApplication Nos. DE 10 2007 012 963.9 filed Mar. 14, 2007 and DE 10 2007050 971.7, filed Oct. 25, 2007. The subject application claims priorityto PCT/EP2008/000606, to German Application Nos. DE 10 2007 012 963.9and DE 10 2007 050 971.7 and incorporates all by reference herein, intheir entirety.

BACKGROUND OF THE INVENTION

The present invention concerns the adsorption arts. More particularly,the present invention concerns high-performance adsorbents based onactivated carbon of high meso- and macroporosity and a process forproduction thereof and also the use of these high-performanceadsorbents, particularly for adsorptive filtering materials, for thefood industry (for example for preparing and/or decolorizing foodproducts, for the adsorption of toxins, noxiants and odors, particularlyfrom gas or air streams, for purifying or cleaning gases, particularlyair, and liquids, particularly water, for application in medicine or tobe more precise pharmacy, and also as sorptive storage mediaparticularly for gases, liquids and the like.

Activated carbon has fairly unspecific adsorptive properties andtherefore is the most widely used adsorbent. Legislation as well as therising sense of responsibility for the environment lead to a risingdemand for activated carbon.

Activated carbon is generally obtained by carbonization (also referredto by the synonyms of smoldering, pyrolysis, burn-out, etc) andsubsequent activation of carbonaceous compounds, preferably suchcompounds as lead to economically reasonable yields. This is because theweight losses through detachment of volatile constituents in the courseof carbonization and through the subsequent burn-out in the course ofactivation are appreciable. For further details concerning theproduction of activated carbon, see for example H.v. Kienle and E.Bäder, Aktivkohle and ihre industrielle Anwendung, Enke VerlagStuttgart, 1980.

The constitution of the activated carbon produced—finely or coarselyporous, firm or brittle, etc—depends on the starting material. Customarystarting materials are coconut shells, charcoal and wood (for examplewood wastes), peat, bituminous coal, pitches, but also particularplastics which play a certain part in the production of woven activatedcarbon fabrics for example.

Activated carbon is used in various forms: pulverized carbon, splintcoal carbon, granulocarbon, molded carbon and also, since the end of the1970s, spherical activated carbon (“spherocarbon”). Spherical activatedcarbon has a number of advantages over other forms of activated carbonsuch as pulverized carbon, splint coal carbon, granulocarbon, moldedcarbon and the like that make it useful or even indispensable forcertain applications: it is free flowing, abrasion resistant or to bemore precise dustless, and hard. Spherocarbon is in great demand forparticular applications, for example, because of its specific form, butalso because of its high abrasion resistance.

Spherocarbon is mostly still being produced today by multistage and verycostly and inconvenient processes. The best known process consists inproducing spherules from bituminous coal tar pitch and suitableasphaltic residues from the petrochemical industry, which are oxidizedto render them unmeltable and then smoldered and activated. For example,spherocarbon can also be produced in a multistage process proceedingfrom bitumen. These multistage processes are very cost intensive and theassociated high cost of this spherocarbon prevents many applicationswherein spherocarbon ought to be preferable by virtue of its properties.

WO 98/07655 A1 describes a process for producing activated carbonspherules wherein a mixture comprising a diisocyanate productiondistillation residue, a carbonaceous processing aid and if appropriateone or more further additives is processed into free-flowing spherulesand subsequently the spherules obtained in this way are carbonized andthen activated.

It is further prior art to produce spherocarbon by smoldering andsubsequent activation of new or used ion exchangers comprising sulfonicacid groups, or by smoldering ion exchanger precursors in the presenceof sulfuric acid and subsequent activation, the sulfonic acid groups andthe sulfuric acid respectively having the function of a crosslinker.Such processes are described for example in DE 43 28 219 A1 and DE 43 04026 A1 and also in DE 196 00 237 A1 including the Germanpatent-of-addition application DE 196 25 069 A1.

However, there are a number of specific applications where it is notonly the geometry or to be more precise the external shape of theactivated carbon which is of decisive importance, but also its porosity,in particular the total pore volume and the adsorption capacity on theone hand and the distribution of the pores, i.e., the fraction ofmicro-, meso- and macropores in relation to the total pore volume, onthe other.

There are a number of applications requiring a particularly high meso-and macroporosity of the activated carbon, i.e., a high meso- andmacropore volume fraction, coupled with an altogether high total porevolume, for example in relation to the applications mentioned at thebeginning, for example for use in the food industry, in the manufactureof certain adsorptive filtering materials (for example for NBCprotective apparel), for the adsorption of toxins, noxiants and odors,particularly from gas or air streams, for purifying or cleaning gases,such as in particular air, and also liquids, for application in medicineor to be more precise pharmacy, in the sorptive storage of gases orliquids and the like.

True, the activated carbon known for this purpose from the prior artdoes have a certain degree of meso- and macroporosity, but that degreeis not sufficient in all cases. In addition, increasing porosity isoften observed to be accompanied by an unwelcome, occasionallyunacceptable decrease in mechanical stability or to be more preciseabrasion resistance. Nor are the fraction of the total pore volume whichis α-counted for by meso- and macropores and the absolute pore volumealways sufficient to ensure adequate performance capability and/or anadequate impregnatability (for example impregnation with metals or metalsalts) for all applications.

BRIEF SUMMARY OF THE INVENTION

This invention relates to high-performance adsorbents based on activatedcarbon in the form of discrete grains of activated carbon having: (a) atleast 70% of the total pore volume formed by pores having pore diametersof more than 20 Å; (b) a measure of central tendency pore diameter (meanpore diameter) of more than 25 Å; (c) a BET surface area of at least1,250 m²/g; and (d) an iodine number of at least 1,250 mg/g. Suchadsorbents typically have a high meso- and macroporosity, (i.e. a highmeso- and macroporous fraction relative to the total pore volume), alarge total pore volume and yet retain high stability to abrasion andbursting.

Further aspects of the present invention relate to a process forproducing the high-performance adsorbents based on activated carbon. Theprocess utilizes a carbonaceous starting material and involves initiallycarbonizing and subsequently activating the starting material. Theactivation step is carried out in two stages. The carbonized startingmaterial is initially subjected, in a first activating step in anatmosphere of water vapor, followed by a second activation step in anatmosphere that includes CO₂.

Further aspects of the present invention relate to a filtering materialbased on the high-performance adsorbents described above.

Still further aspects of the present invention relate to a piece ofprotective apparel that includes the high-performance adsorbentsdescribed above.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph illustrating a N₂ adsorption isotherm for a firsthigh-performance adsorbent of the present invention.

FIG. 2 is a graph illustrating a N₂ adsorption isotherm for a secondhigh-performance adsorbent of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

It is therefore an object of the present invention to provide, on thebasis of activated carbon, a high-performance adsorbent which issuitable for the aforementioned fields of application in particular andwhich at least substantially avoids or else at least ameliorates theabove-described disadvantages of the prior art. More particularly, theadsorbent to be provided according to the present invention should havea high meso- and macroporosity, i.e., a high meso- and macroporousfraction in relation to the total pore volume and also a large totalpore volume, yet at the same time also good mechanical stability,particularly a high stability to abrasion and bursting.

In the context of the present invention, the term “micropores” refers topores having pore diameters of up to 20 Å inclusive, whereas the term“mesopores” refers to pores having pore diameters in the range of morethan 20 Å (i.e., >20 Å) to 500 Å inclusive and the term “macropores”refers to pores having pore diameters of more than 500 Å (i.e., >500 Å):

-   -   micropores: pore diameter_(micropores)≧20 Å    -   mesopores: 20 Å<pore diameter_(mesopores)≦500 Å    -   macropores: pore diameter_(macropores)>500 Å

By way of a solution to the problem described above, the presentinvention proposes—in accordance with a first aspect of the presentinvention—high-performance adsorbents based on activated carbon in theform of discrete grains of activated carbon, preferably in sphericalform, according to claim 1. Further, in particular advantageousembodiments of the high-performance adsorbents of the present inventionare subject matter of the corresponding subclaims.

The present invention further provides—in accordance with a secondaspect of the present invention—the present invention process forproducing the high-performance adsorbents according to the presentinvention, as more particularly defined in the corresponding processclaims.

The present invention yet further provides—in accordance with a thirdaspect of the present invention—the present invention use of thehigh-performance adsorbents according to the present invention, as moreparticularly defined in the corresponding use claims.

The present invention accordingly provides—in accordance with a firstaspect of the present invention—high-performance adsorbents based onactivated carbon in the form of discrete grains of activated carbon,preferably in spherical form, these high-performance adsorbents beingcharacterized by the following parameters:

-   -   a pore volume fraction formed by pores having pore diameters of        more than 20 Å (i.e., in other words, a meso- and macropore        volume fraction) which comprises at least 55% of the total pore        volume of high-performance adsorbents (This parameter is        interchangeably also referred to as “fraction of external pore        volume in relation to total pore volume”.),    -   a measure of central tendency pore diameter of more than 25 Å.    -   a BET surface area of at least 1250 m²/g,

The present high-performance adsorbents or to be more precise activatedcarbons, in addition to the aforementioned properties or to be moreprecise parameters, particularly a high meso- and macropore volumefraction (i.e., a high pore volume fraction due to pores having a porediameter of more than 20 Å), are further notable in particular for alarge total porosity and a simultaneously large BET surface area.

As will be shown in what follows, the mechanical strength, particularlythe abrasion resistance and the bursting or to be more precisecompressive strength, of the present high-performance adsorbents isdespite the high total porosity extremely high—in contrast to comparablehigh-porosity activated carbons of the prior art—so that the presenthigh-performance adsorbents or to be more precise activated carbons arealso suitable for applications where they are exposed to largemechanical loads.

In relation to all the parameter indications hereinabove andhereinbelow, it is to be noted that the recited limits, in particularupper and lower limits, are included, i.e., all statements of values areto be understood as including the respective limits, except whereotherwise stated in an individual case. It will further be understoodthat in an individual case or in relation to an application it may benecessary if appropriate to depart slightly from the limits mentionedwithout leaving the realm of the present invention.

The hereinabove and hereinbelow mentioned parameter data are determinedusing standardized or explicitly indicated methods of determination orusing methods of determination familiar per se to one skilled in theart.

The parameter data concerning the characterization of the porosity,particularly of the above-specified meso- and macropore fraction (i.e.,the fraction of the total pore volume of the high-performance adsorbentswhich is contributed by pores having pore diameters of more than 20 Å)each follow from the nitrogen isotherm of the activated carbon measured.

The measure of central tendency pore diameter is similarly determined onthe basis of the respective nitrogen isotherms.

The BET method of determining the specific surface area is in principleknown as such to one skilled in the art, so that no further details needbe furnished in this regard. All BET surface area data are based on theASTM D6556-04 method of determination. The present invention utilizesthe MultiPoint BET (MP-BET) method of determination in a partialpressure range p/p₀ of 0.05 to 0.1.

With regard to further details concerning the determination of the BETsurface area or to be precise concerning the BET method, reference maybe made to the aforementioned ASTM D6556-04 standard and also to RömppChemielexikon, 10th edition, Georg Thieme Verlag, Stuttgart/New York,headword: “BET-Methode”, including the references cited therein, and toWinnacker-Küchler (3rd edition), Volume 7, pages 93 ff, and also to Z.Anal. Chem. 238, pages 187 to 193 (1968).

As observed above and more particularly specified hereinbelow, onespecial feature of the high-performance adsorbents of the presentinvention is that they have a very large total pore volume as determinedby the Gurvich method, to provide a very large adsorptive capacity inwhich the meso- and macropore volume fraction (i.e., that is, the porevolume fraction due to pores having pore diameters above 20 Å) is high,viz. at least 55% of the total pore volume.

The Gurvich determination of total pore volume is a method ofmeasurement/determination known per se in this field to a person skilledin the art. For further details concerning the Gurvich determination oftotal pore volume reference may be made for example to L. Gurvich(1915), J. Phys. Chem. Soc. Russ. 47, 805, and also to S. Lowell et al.,Characterization of Porous Solids and Powders: Surface Area Pore Sizeand Density, Kluwer Academic Publishers, Article Technology Series,pages 111 et seq.

The Gurvich total pore volume of the high-performance adsorbents of thepresent invention is at least 0.8 cm³/g, particularly at least 1.0cm³/g, preferably at least 1.2 cm³/g, and can generally attain values ofup to 2.0 cm³/g, particularly up to 2.5 cm³/g, preferably up to 3.0cm³/g, more preferably up to 3.5 cm³/g.

The Gurvich total pore volume of the high-performance adsorbents of thepresent invention is generally in the range from 0.8 to 3.5 cm³/g,particularly 1.0 to 3.5 cm³/g, preferably 1.2 to 3.2 cm³/g.

Owing to their high meso- and macroporosity, the meso- and macroporevolume of the high-performance adsorbents of the present invention(i.e., that is, in other words, the pore volume formed by pores havingpore diameters of more than 20 Å) is relatively high in that in generalthe carbon black method pore volume of the high-performance adsorbentsof the present invention which is formed by pores having pore diametersof more than 20 Å (i.e., that is, the meso- and macropore volume) is inthe range from 0.4 to 3.3 cm³/g, particularly 0.8 to 3.2 cm³/g,preferably 1.0 to 3.1 cm³/g, more preferably 1.2 to 3.0 cm³/g, mostpreferably 1.2 to 2.8 cm³/g. The pore volume formed by pores having porediameters of more than 20 Å is interchangeably also referred to as“external pore volume”.

Generally at least 60%, particularly at least 65%, preferably at least70%, more preferably at least 75%, most preferably at least 80% of thetotal pore volume of the high-performance adsorbents of the presentinvention is formed by the pore volume of pores having pore diameters ofmore than 20 Å (i.e., that is, in other words, by the meso- andmacropore volume).

Generally 55% to 95%, particularly 60% to 95%, preferably 65% to 90%,more preferably 70 to 85% of the total pore volume of thehigh-performance adsorbents of the present invention is formed by thepore volume of pores having pore diameters of more than 20 Å. Theaforementioned percentages thus identify that proportion of the totalpore volume of the high-performance adsorbents of the present inventionwhich is attributable to the fraction of the so-called external porevolume (i.e., the pore volume formed by pores having pore diameters ofmore than 20 Å).

The carbon black method of determination is known per se to one skilledin the art (as is the corresponding analysis, including plotting andfixing of the p/p_(o) range), so that no further details are needed inthis regard. In addition, for further details of the carbon black methodof determining the pore surface area and the pore volume reference maybe made for example to R. W. Magee, Evaluation of the External SurfaceArea of Carbon Black by Nitrogen Adsorption, Presented at the Meeting ofthe Rubber Division of the American Chem. Soc., October 1994, forexample cited in: Quantachrome Instruments, AUTOSORB-1, AS1 WinVersion1.50, Operating Manual, OM, 05061, Quantachrome Instruments 2004,Florida, USA, pages 71 ff.

Owing to the high meso- and macroporosity of the high-performanceadsorbents of the present invention, the measure of central tendencypore diameter is relatively high in that in general it is at least 30 Å,particularly at least 35 Å, preferably at least 40 Å.

In general, the measure of central tendency pore diameter of thehigh-performance adsorbents of the present invention is in the rangefrom 25 to 75 Å, particularly 30 to 75 Å, preferably 35 to 70 Å, morepreferably 40 to 65 Å.

As stated above, it is a further special feature of the high-performanceadsorbents of the present invention that BET surface area is relativelylarge and that it is at least 1250 m²/g, preferably at least 1400 m²/g,more preferably at least 1500 m²/g, most preferably at least 1600 m²/g.

In general, the BET surface area of the high-performance adsorbents ofthe present invention is in the range from 1250 m²/g to 2800 m²/g,particularly 1400 to 2500 m²/g, preferably 1500 to 2300 m²/g, morepreferably 1600 to 2100 m²/g.

The carbon black method external pore surface area of thehigh-performance adsorbents of the present invention (i.e., that is, thepore surface area formed by pores having pore diameters of more than 20Å) is relatively large, because of the high meso- and macroporefraction, and is generally in the range from 200 to 1000 m²/g,particularly 250 to 950 m²/g, preferably 350 to 900 m²/g, morepreferably 400 to 850 m²/g.

In general, the carbon black method external pore surface area of thehigh-performance adsorbents of the present invention (i.e., that is, thepore surface area formed by pores having pore diameters of more than 20Å) forms up to 30%, particularly up to 40%, preferably up to 50% of thetotal pore surface area of the high-performance adsorbents of thepresent invention. More particularly, the carbon black method externalpore surface area of the high-performance adsorbents of the presentinvention (i.e., that is, the pore surface area formed by pores havingpore diameters of more than 20 Å) forms 10 to 50%, particularly 15 to45%, preferably 20 to 40% of the total pore surface area of thehigh-performance adsorbents of the present invention.

In addition, the high-performance adsorbents of the present inventionhave an extremely high butane adsorption and simultaneously an extremelyhigh iodine number, which fact characterizes their property of havingexcellent adsorption properties with regard to a wide variety ofmaterials to be adsorbed.

The ASTM D5742-95/00 butane adsorption of the high-performanceadsorbents of the present invention is generally at least 30%,particularly at least 35%, preferably at least 40%. In general, thehigh-performance adsorbents of the present invention have an ASTMD5742-95/00 butane adsorption in the range from 30% to 80%, particularly35 to 75% preferably 40 to 70%.

The ASTM D4607-94/99 iodine number of the high-performance adsorbents ofthe present invention is generally at least 1250 mg/g, particularly atleast 1300 mg/g, preferably at least 1350 mg/g. The high-performanceadsorbents of the present invention preferably have an ASTM D4607-94/99iodine number in the range from 1250 to 2100 mg/g, particularly 1300 to2000 mg/g, preferably 1350 to 1900 mg/g. The iodine number can be takenas a measure for available surface area provided by predominantly largermicropores; the aforementioned values of the iodine number of thehigh-performance adsorbents of the present invention show that thehigh-performance adsorbents of the present invention simultaneously alsohave a high microporosity.

Owing to their high meso- and macroporosity, the high-performanceadsorbents of the present invention similarly have high methylene blueand molasses adsorption numbers which together can be taken as a measureof available surface area provided predominantly by meso- andmacropores. The methylene blue number or to be more precise themethylene blue adsorption, which indicates the amount of methylene blueadsorbed per defined amount of adsorbents, under defined conditions(i.e., the number of ml of a methylene blue standard solutiondecolorized by a defined amount of dry and pulverized adsorbents),relates to larger micropores and predominantly smaller mesopores andgives an indication of the adsorptive capacity of the high-performanceadsorbents of the present invention in relation to molecules comparablein size to methylene blue. By contrast, the molasses number must beconsidered a measure of the meso- and macroporosity and indicates theamount of adsorbents which is required to decolorize a standard molassessolution, so that the molasses number gives an indication of theadsorptive capacity of the high-performance adsorbents of the presentinvention in relation to molecules that are comparable in size tomolasses (generally sugar beet molasses). Together, therefore, themethylene blue and molasses numbers can be considered a measure of themeso- and macroporosity of the high-performance adsorbents of thepresent invention.

The methylene blue value of the high-performance adsorbents of thepresent invention which is determined by following the method of CEFIC(Conseil Européen des Féderations des Industries Chimiques, AvenueLouise 250, Bte 71, B—1050 Brussels, November 1986, European Council ofChemical Manufacturers' Federations, Test Methods for Activated Carbons,Item 2.4 “Methylene blue value”, pages 27/28) is at least 15 ml,particularly at least 17 ml, preferably at least 19 ml, and is generallyin the range from 15 to 60 ml, particularly 17 to 50 ml, preferably 19to 45 ml.

The methylene blue value according to the aforementioned CEFIC method isthus defined as the number of ml of a methylene blue standard solutionwhich are decolorized by 0.1 g of dry and pulverized activated carbon.Performing this method requires a glass vessel with ground stopper, afilter and also a methylene blue standard solution prepared as follows:1200 mg of pure methylene blue dye (corresponding to about 1.5 g ofmethylene blue to DAB VI [German Pharmacopeia, 6th edition] orequivalent product) are dissolved in water in a 1000 ml volumetricflask, and the solution is allowed to stand for several hours orovernight; to check its strength, 5.0 ml of the solution are dilutedwith 0.25% (volume fractions) acetic acid to 1.0 l in a volumetric flaskand thereafter the absorbance is measured at 620 nm and 1 cm pathlength, and it has to be 0.840±0.010. If the absorbance is higher, ithas to be diluted with the computed amount of water; if it is lower, thesolution is discarded and made up fresh. By way of sample preparation,the high-performance adsorbents in the form of granular activated carbonare pulverized (<0.1 mm) and then dried to a constant weight at 150° C.Precisely 0.1 g of the spherocarbon is then combined with 25 ml (5 ml)of the methylene blue standard solution in a ground glass flask (Apreliminary test has to be carried out to see whether an initialaddition of 25 ml of methylene blue standard solution with 5 mladditions or an initial addition of 5 ml of methylene blue standardsolution with 1 ml additions can be used.). The flask is shaken untildecolorization occurs. Then, a further 5 ml (1 ml) of the methylene bluestandard solution are added, and the flask is shaken to the point ofdecolorization.

The addition of methylene blue standard solution is repeated in 5 mlamounts (1 ml amounts) as long as decolorization still occurs within 5minutes. The entire volume of the test solution decolorized by thesample is recorded. The test is repeated to confirm the resultsobtained. The volume of the methylene blue standard solution in ml whichare just decolorized is the methylene blue value of the high-performanceadsorbents. It is to be noted in this connection that the methylene bluedye must not be dried, since it is heat sensitive; rather, the watercontent must be corrected for purely arithmetically.

The dimensionless molasses number can in principle be determined eitherby following the Norit method (Norit N. V., Amersfoort, Netherlands,Norit Standard Method NSTM 2.19 “Molasses Number (Europe)”) oralternatively by following the PACS method (PACS=Professional Analyticaland Consulting Services Inc., Coraopolis Pa., USA). In the context ofthe present invention, the values of the molasses number are determinedby following the PACS method. Thus, the PACS method molasses number ofthe high-performance adsorbents of the present invention is at least300, particularly at least 350, preferably at least 400, and isgenerally in the range from 300 to 1400, particularly 350 to 1300,preferably 400 to 1250, most preferably 700 to 1200.

Whether by following the Norit method or by following the PACS method,the molasses number is determined by determining the amount ofpulverized high-performance adsorbents based on activated carbon that isneeded to decolorize a standard molasses solution. Determination iseffected photometrically, and the standard molasses solution isstandardized against a standardized activated carbon having a molassesnumber of 245 and/or 350. For further details in this regard, referencecan be made to the two aforementioned prescriptive methods.

Despite their high porosity, particularly meso- and macroporosity, thehigh-performance adsorbents of the present invention have a highcompressive or bursting strength (resistance to weight loading) and alsoan extremely high abrasion resistance.

The compressive or bursting strength (resistance to weight loading) pergrain of activated carbon, in particular per spherule of activatedcarbon, is thus at least 5 newtons, in particular at least 10 newtonsand preferably at least 15 newtons. In general, the compressive orbursting strength (resistance to weight loading) per grain of activatedcarbon, particularly per spherule of activated carbon, ranges from 5 to50 newtons, in particular from 10 to 45 newtons and preferably from 15to 40 newtons.

As mentioned, the abrasion hardness of the high-performance adsorbentsof the present invention is also extremely high in that the abrasionresistance when measured by the method of CEFIC (Conseil Europeen desFéderations des Industries Chimiques, Avenue Louise 250, Bte 71, B—1050Brussels, November 1986, European Council of Chemical Manufacturers'Federations, Test Methods for Activated Carbons, Item 1.6 “MechanicalHardness”, pages 18/19) is always 100% or virtually 100%. Similarly,when measured according to ASTM D3802 abrasion resistances of thehigh-performance adsorbents of the present invention of 100% orvirtually 100% are always obtained.

Therefore, the applicant company has developed a modified test method onthe lines of this CEFIC method in order that more meaningful values maybe obtained. The modified method of determination provides a bettersimulation of the resistance of the sample or to be more precise of thehigh-performance adsorbents to abrasion or attrition under near actualservice conditions. For this purpose, the sample is exposed tostandardized conditions for a defined time in a horizontally swinginggrinding cup charged with a tungsten carbide ball. The procedure adoptedfor this purpose is as follows: 200 g of a sample are dried for one hourat (120±2)° C. in a circulating air drying cabinet (type: Heraeus UT6060 from Kendro GmbH, Hanau) and are subsequently cooled down in adesiccator over drying agent to room temperature. 50 g of the driedsample are removed and sieved off by means of a sieving machine equippedwith an analytical sieve (for example, type: AS 200 control from RetschGmbH, Hanau) at a swing amplitude of 1.2 mm for ten minutes through ananalytical sieve, the analytical sieve being selected depending on thegrain distribution of the sample to be measured (for example, analyticalsieve of mesh size: 0.315 mm, diameter: 200 mm, height: 50 mm); thesubsize grain is discarded. 5 ml of the nominal grain are filled into a10 ml graduated cylinder to DIN ISO 384 (volume: 10 ml, height: 90 mm)and the weight is accurately determined to 0.1 mg using an analyticalbalance (type: BP121S from Sartorius AG, Gottingen, weighing range: 120g, accuracy class: E2, readability: 0.1 mg) by means of a weighing glasshaving a ground glass lid (volume: 15 ml, diameter: 35 mm, height: 30mm) The weighed sample is placed together with a tungsten carbidegrinding ball of 20 mm diameter in a 25 ml grinding cup with screwaction closure (volume: 25 ml, diameter: 30 mm, length: 65 mm, materialof construction: stainless steel) and then the abrasion test is carriedout by means of a swing mill (type: MM301 from Retsch GmbH, Haan, swingmill with grinding cup); the grinding cup swings in a horizontalposition for one minute at a frequency of 10 Hz in the swing mill,causing the grinding ball to impact on the sample and thus createabrasion. Subsequently, the sample is sieved off by means of a sievingmachine at a swing amplitude of 1.2 mm for five minutes through theaforementioned analytical sieve, the subsize grain again being discardedand the nominal grain, which is dependent on the grain distribution ofthe relevant sample (e.g. nominal grain greater than 0.315 mm), beingweighed back accurately to 0.1 mg in the weighing glass with lid. Theabrasion hardness is computed as a mass fraction in % by the followingformula: abrasion hardness [%]=(100×back-weighed weight [g])/originalweight [g].

According to this method of determination, modified by the applicantcompany by modifying the aforementioned CEFIC standard, the abrasionresistance of the high-performance adsorbents of the present inventionis at least 75%, particularly at least 80%, preferably at least 85%,more preferably at least 90%, most preferably at least 95%.

As stated above, it is a further special feature of the high-performanceadsorbents of the present invention that they also have a certain degreeof microporosity and thus also a certain micropore surface area (i.e.surface area which is formed by pores having pore diameters of ≦20 Å. Ingeneral, the carbon black method micropore surface area of thehigh-performance adsorbents of the present invention which is formed bypores having pore diameters of ≦20 Å is at least 1000 m²/g, particularlyat least 1100 m²/g, preferably at least 1200 m²/g, and is generally inthe range from 1000 to 1800 m²/g, particularly 1100 to 1600 m²/g,preferably 1200 to 1500 m²/g.

In general, the carbon black method micropore surface area of thehigh-performance adsorbents of the present invention which is formed bypores having pore diameters of ≦20 Å is at least 30%, particularly atleast 40%, preferably at least 50% of the total pore surface area of thehigh-performance adsorbents of the present invention. More particularly,the carbon black method micropore surface area of the high-performanceadsorbents of the invention which is formed by pores having porediameters of ≦20 Å is in the range from 50 to 90%, particularly 55 to85%, preferably 60 to 80% of the total pore surface area of thehigh-performance adsorbents of the present invention.

Similarly, the weight- and volume-based volume V_(ads) (N₂) of thehigh-performance adsorbents of the present invention at differentpartial pressures p/p₀ is very large:

The weight-based adsorbed N₂ volume V_(ads(wt)) of the high-performanceadsorbents of the present invention, determined at a partial pressurep/p₀ of 0.25, is at least 300 cm³/g, particularly at least 350 cm³/g,preferably at least 375 cm³/g, and is particularly in the range from 300to 800 cm³/g, preferably 350 to 700 cm³/g, more preferably 375 to 650cm³/g.

In general, the volume-based adsorbed N₂ volume V_(ads(vol)) of thehigh-performance adsorbents of the present invention, determined at apartial pressure p/p₀ of 0.25, is at least 75 cm³/cm³, particularly atleast 100 cm³/cm³, and is particularly in the range from 75 to 300cm³/cm³, preferably 80 to 275 cm³/cm³, more preferably 90 to 250cm³/cm³.

In general, the weight-based adsorbed N₂ volume V_(ads(wt)) of thehigh-performance adsorbents of the present invention, determined at apartial pressure p/p₀ of 0.995, is at least 400 cm³/g, particularly atleast 450 cm³/g, and is particularly in the range from 400 to 2300cm³/g, preferably 450 to 2200 cm³/g, more preferably 750 to 2100 cm³/g.

In general, the volume-based adsorbed N₂ volume V_(ads(vol)) of thehigh-performance adsorbents of the present invention, determined at apartial pressure p/p₀ of 0.995, is at least 200 cm³/cm³, particularly atleast 250 cm³/cm³, and is particularly in the range from 200 to 500cm³/cm³, preferably 250 to 400 cm³/cm³, more preferably 275 to 380cm³/cm³.

The high-performance adsorbents of the present invention are based ongranular, in particular spherical, activated carbon whose measure ofcentral tendency particle diameter, determined to ASTM D2862-97/04, isgenerally in the range from 0.01 to 2.0 mm, particularly 0.01 to 1.0 mm,preferably 0.05 to 0.09 mm, more preferably 0.1 to 0.8 mm, mostpreferably 0.15 to 0.7 mm.

The ash content of the high-performance adsorbents of the presentinvention, determined to ASTM D2866-94/04, is at most 1%, particularlyat most 0.8%, preferably at most 0.6%, more preferably at most 0.5%.

The ASTM D2867-04/04 moisture content of the high-performance adsorbentsof the present invention is at most 1%, particularly at most 0.5%,preferably at most 0.2%.

The high-performance adsorbents of the present invention generally havea bulk density, determined to ASTM B527-93/00, in the range from 150 to750 g/l, particularly 175 to 650 g/l, preferably 200 to 600 g/l.

In accordance with a particular embodiment of the present invention, thepresent invention provides high-performance adsorbents based onactivated carbon in the form of discrete grains of activated carbon,preferably in spherical form, particularly as described above,characterized by the following parameters:

-   -   a pore volume fraction formed by pores having pore diameters of        more than 20 Å which comprises at least 55% of the total pore        volume of the high-performance adsorbents,    -   a measure of central tendency pore diameter of more than 25 Å.    -   a BET surface area of at least 1250 m²/g,    -   a methylene blue value of at least 15 ml, and    -   a molasses number of at least 300.

The present invention further provides—in accordance with a secondaspect of the present invention—the present invention process forproducing the high-performance adsorbents according to the presentinvention. In accordance with this aspect of the present invention, thepresent invention accordingly provides a process for producing theabove-described high-performance adsorbents based on activated carbon,which process comprises a carbonaceous starting material being initiallycarbonized and subsequently activated, wherein the activation is carriedout in two stages, wherein the carbonized starting material is initiallysubjected, in a first activating step, to an activation in an atmospherecomprising water vapor, followed by a second activating step ofactivation in an atmosphere comprising CO₂.

The high-performance adsorbents of the present invention are producedusing carbonaceous starting materials, in particular sulfonatedstyrene-divinylbenzene copolymers, particularly sulfonateddivinylbenzene-crosslinked polystyrenes, preferably in grain form, morepreferably in spherical form. The divinylbenzene content of thesulfonated styrene-divinylbenzene copolymers used as starting materialsto produce the high-performance adsorbents of the present inventionshould particularly be in the range from 1 to 20% by weight,particularly 1 to 15% by weight, preferably 2 to 10% by weight, based onthe styrene-divinylbenzene copolymers. The starting copolymers can inprinciple be selected from the gel type or else from the macroporoustype. When unsulfonated starting materials are used, the sulfonation canbe carried out in situ (in particular before and/or during thecarbonization), particularly using methods known per se to one skilledin the art, preferably by means of sulfuric acid and/or oleum and/orSO₃; this is familiar per se to one skilled in the art (cf. also theprior art described at the beginning). Starting materials which haveproven particularly advantageous are the gel-form or macroporous typesof the corresponding ion exchange resins or of the correspondingunsulfonated precursors of ion exchange resins which still have to besulfonated.

The carbonization (also known by the synonyms of pyrolysis, burn-out orsmoldering) converts the carbonaceous starting polymers to carbon; thatis, in other words, the carbonaceous starting material is carbonized.Carbonization of the aforementioned organic polymeric grains, inparticular polymeric spherules, based on styrene and divinylbenzenewhich comprise sulfonic acid groups leads to the detachment of thesulfonic acid groups during the carbonization to free radicals and thusto crosslinks without which there would be no pyrolysis residue(=carbon). In general, the carbonization is carried out under an inertatmosphere (for example nitrogen) or an at most slightly oxidizingatmosphere. It can similarly be advantageous for the inert atmosphere ofthe carbonization, in particular if it is carried out at comparativelyhigh temperatures (for example in the range from about 500 to 650° C.)to be admixed with a minor amount of oxygen, in particular in the formof air (for example 1 to 5%) in order that an oxidation of thecarbonized polymeric skeleton may be effected and the subsequentactivation may thereby be facilitated. In general, the carbonization iscarried out at temperatures of 100 to 950° C., particularly 150 to 900°C., preferably 300 to 850° C. The total duration of the carbonization isapproximately 30 minutes to approximately 10 hours, particularlyapproximately 1 hour to approximately 6 hours.

Following the carbonization, the carbonized intermediate product issubjected to an activation resulting, at the end of which, in thepresent invention's high-performance adsorbents based on activatedcarbon in grain form, in particular spherical form. The basic principleof the activation is to degrade a portion of the carbon generated duringthe carbonization, selectively and specifically under suitableconditions. This gives rise to numerous pores, fissures and cracks, andthe surface area per unit mass increases appreciably. Activation thusinvolves a specific burn-out of the carbon. Since carbon is degraded inthe course of activation, this operation goes hand in hand with a lossof substance which—under optimal conditions—is equivalent to an increasein the porosity and in the internal surface area and in the pore volume.Activation is therefore carried out under selective or to be moreprecise policed oxidizing conditions.

The special feature of how the high-performance adsorbents of thepresent invention are produced, as well as the selection of the startingmaterial described above, resides in the specific management of theactivation process, in particular in the twostageness of the activationprocess, wherein the carbonized starting material is initiallysubjected, in a first activating step, to an activation in an atmospherecomprising water vapor, followed by a second activating step in anatmosphere comprising CO₂. As the studies carried out by the applicanthave determined it is surprisingly only the separate performance ofthese activating steps in the aforementioned order that leads to thedesired products. Reversing the order of the activating steps, or oneconjointly conducted activating step in a water vapor/carbon dioxideatmosphere leads in contrast to distinctly less performance-capableproducts which do not have the desired properties, particularly not thehigh total porosity coupled with high meso-/macropore content and arelatively high absolute micropore volume and also high mechanicalstability. As the studies by the applicant company have surprisinglyshown when the process is carried out according to the present inventionwater vapor activation leads predominantly to the formation of themicropore fraction, while carbon dioxide activation contributespredominantly to formation of the meso- and macropores, and surprisinglythe formation of the meso- and macropore volume is not at the expense ofthe micropore volume, or vice versa. What is therefore novel andsurprising is in total that this produces a very large total pore volumecoupled with very high stability and abrasion resistance and also veryhigh meso- and macropore fraction coupled with simultaneously highmicropore fraction (i.e., the formation of meso- and macropores to theenormous extent in the products of the present invention does not leadto a reduction in the micropore fraction, as customary in the priorart). On the contrary, a high micropore fraction is achieved while themeso-/macropore volume fraction is also high at the same time.

The general procedure is for the first activating step to be carried outat temperatures of 700 to 1300° C., particularly 800 to 1200° C.,preferably 850 to 950° C., and/or for a duration of 5 to 24 hours,preferably 5 to 15 hours, particularly 6 to 12 hours. Usually, theduration of the first activation stage can be controlled as a functionof the attainment of a predetermined iodine number; for example, thefirst activation stage can be carried out to attainment of an iodinenumber of at least 1000 mg/g, particularly at least 1250 mg/g. Theatmosphere of the first activation stage comprises water vapor,particularly a mixture of water vapor/inert gas, preferably a mixture ofwater vapor/nitrogen, or consists thereof. For the aforementionedreasons, the presence of activating gases other than water vapor,particularly the presence of carbon oxides (CO₂ for example), oxygenand/or ammonia, must be foreclosed in the context of the firstactivation stage. Good results are obtained when the throughput or to bemore precise the amount used of water vapor is 25 to 350 l/h,particularly 50 to 300 l/h, reckoned as water (i.e., liquid water at 25°C. and under atmospheric pressure). Depending on the amount of startingmaterial to be activated (=carbonisate previously produced bycarbonization), the amount used or the mass-based throughput of watervapor should advantageously be 0.01 to 50 l/(h·kg), particularly 0.02 to25 l/(h·kg), preferably 0.02 to 5 l/(h·kg), reckoned as water (i.e.,liquid water at 25° C. and under atmospheric pressure) and based onstarting material to be activated with water vapor.

The general procedure for the second activating step is for the secondactivating step to be carried out at temperatures of 700 to 1300° C.,particularly 800 to 1200° C., preferably 850 to 950° C., and/or for aduration of 1 to 10 hours, particularly 3 to 8 hours. The atmosphere ofthe second activation stage comprises CO₂, particularly pure CO₂ or amixture of CO₂/inert gas, particularly a mixture of CO₂/nitrogen, orconsists thereof, and pure carbon dioxide is particularly preferred. Forthe aforementioned reasons, the presence of activating gases other thanCO₂, in particular the presence of water vapor, must be foreclosed inthe context of the second activation stage. Good results are obtainedwhen the throughput or the amount used of CO₂ is 10 to 250 m³/h,particularly 20 to 200 m³/h (based on pure CO₂). Depending on the amountof starting material to be activated, the amount used or the mass-basedthroughput of CO₂ should advantageously be 0.001 to 100 m³/(h·kg),particularly 0.01 to 50 m³/(h·kg), preferably 0.05 to 10 m³/(h·kg),reckoned as pure gaseous CO₂ under activating conditions, particularlyat the respective pressure and the respective temperature, which areselected for the activation, and based on starting material to beactivated with CO₂.

The process is typically carried out such that the first and secondactivation stages merge into each other (for example by changing theactivating atmosphere within the same apparatus).

What is surprising is in particular that, first, the way the activationis carried out according to the present invention provides exact controlof the porosity with regard to the micro-, meso- and macropore fractionsand, secondly, that an extremely high abrasion resistance and mechanicalcompressive strength result despite the high porosity coupled withsimultaneously high meso- and macroporosity and also good microporosity.It was unforeseeable that this approach selectively generates high meso-and macroporosity coupled with simultaneously sufficient microporosity.

Porosity can be adjusted or controlled to specific values by varying thepreviously specified activating conditions. The high-performanceadsorbents of the present invention can thus be custom tailored so tospeak. High-performance adsorbents based on activated carbon whichcombine high meso- and macroporosity with good microporosity and alsohigh stability and abrasion resistance are not known from the prior art.Another welcome aspect is the excellent adsorption behavior to moleculesof virtually any desired molecular size due to the presence of all kindsof pores in relatively large amounts or fractions. Similarly welcome isthe excellent impregnatability of the products of the present inventionwith catalysts or to be more precise metals or metal salts.

The graphs in FIG. 1 and FIG. 2 show N₂ adsorption isotherms for twodifferent high-performance adsorbents of the present invention, whichwere produced under different activating conditions. Thephysical-chemical properties of the two high-performance adsorbents ofthe present invention are also summarized in Table 1 below. Forcomparison, a commercially available activated carbon from Kureha isalso listed therein with the physical-chemical properties in question.

The data reported in Table 1 show the superiority of thehigh-performance adsorbents of the present invention over a prior artactivated carbon: The combination of high total porosity with highmeso-/macropore volume fraction at high BET surface area and also goodabsolute microporosity, high mechanical durability and excellentadsorption properties is in this combination—as well as the otherphysical-chemical parameters—only to be found in the high-performanceadsorbents of the present invention. The present invention thus makes itpossible to produce high-performance adsorbents based on activatedcarbon in grain form, in particular spherical form, which are superiorto commercially available products.

The inventive high-performance adsorbents “activated carbon I” and“activated carbon II” recited in Table 1 are each produced as follows:commercially available dried ion exchanger precursors based ondivinylbenzene-crosslinked polystyrene copolymers having adivinylbenzene content of about 4% are sulfonated in a conventionalmanner at temperatures of 100° C. to 150° C. using a sulfuric acid/oleummixture. This is followed in a conventional manner by carbonization attemperatures up to 850° C. for four hours under nitrogen andsubsequently the induction of activation. Inventive activated carbon Iwas produced by performing the first activation stage (“water vaporactivation”) for a duration of about 8.5 hours at about 900° C. with awater vapor throughput of about 100 m³/h and the second activation stage(“carbon dioxide activation”) for a duration of about 8.0 hours at about900° C. with a carbon dioxide throughput of about 35 m³/h; in contrast,inventive activated carbon II was produced by performing the firstactivation stage (“water vapor activation”) for a duration of about 10.5hours at about 925° C. with a water vapor throughput of about 125 m³/hand the second activation stage (“carbon dioxide activation”) for aduration of about 8 hours at about 925° C. with a carbon dioxidethroughput of about 40 m³/h. After cooling down to room temperature, theinventive products recited in Table 1 are obtained.

TABLE 1 Comparison of physical-chemical parameters of two inventivehigh-performance adsorbents based on spherical activated carbon on theone hand and commercially available activated carbon in spherical formfrom Kureha on the other Inventive activated carbon I Inventiveactivated carbon II After second After second After first activatingactivating After first activating activating Commercially step(intermediate step (end step (intermediate step (end available activatedproduct) product) product) product) carbon from Kureha Total pore volume(Gurvich) (p/p₀ = 0.6267 1.7890 0.7510 3.1590 0.5891 0.995) [cm³/g]**Measure of central tendency pore diameter 18.08 42.05 19.05 62.75 17.89[Å] BET (Multipoint, MP) (p/p₀ = 0.05-0.1) 1.387 1.702 1.577 2.013 1.317(ASTM D6556-04) [m²/g]** Carbon black method micropore volume 0.55240.5082 0.6211 0.5311 0.5240 [cm³/g]* Micropore fraction of total porevolume 88.1 28.4 82.7 16.8 88.95 [%]* Adsorbed N₂ volume (p/p₀ = 0.25)weight 368 463 422 563 349 based [cm³/g]** Adsorbed N₂ volume (p/p₀ =0.25) volume 233 138 227 101 206 based [cm³/cm³]** Adsorbed N₂ volume(p/p₀ = 0.995) 404 1154 484 2037 380 weight based [cm³/g]** Adsorbed N₂volume (p/p₀ = 0.995) volume 256 344 261 365 224 based [cm³/cm³]**Carbon black micropore surface area 1342 1261 1499 1288 1271 [cm²/g]*Carbon black meso-plus macropore volume 0.0743 1.2808 0.1299 2.6279 0.07(= so-called external pore volume) [cm³/g]*** Fraction of meso- andmacropores in total 11.9 71.6 17.3 83.2 11.1 pore volume (= fraction ofso-called external pore volume in relation to total pore volume) [%]***Carbon black surface area of meso- and 45 441 78 725 46 macropores (=so-called external pore surface area) [cm²/g]*** Pore surface areafraction of meso- and 3.2 25.9 4.9 36.0 3.5 macropores in relation toBET surface area (= proportion of so-called external pore surface areain relation to BET surface area) (MP) [%]*** Adsorbate N₂ N₂ N₂ N₂ N₂Butane adsorption (ASTM D5742-95/00) 30.9 42.4 35.4 52.9 29.2 [%] Iodinenumber 1413 1588 1490 1750 1343 (ASTM D4607-94/99) [mg/g] Methylene bluenumber (CEFIC) [ml] 19.9 34.8 27.2 38.9 <10 Molasses number (PACS)[dimension- 96 1020 142 1174 <100 less] Abrasion resistance (internalmethod) [%] 98.22 90.38 99.2 90.04 <90 *micropores: pores having porediameters ≦20 Å **p/p₀ = partial pressure or partial pressure range***meso- and macropores: collective term for all pores with porediameters >20 Å

The present invention further provides—in accordance with a third aspectof the present invention—the present invention use of thehigh-performance adsorbents according to the present invention.

The high-performance adsorbents of the present invention areparticularly useful for the adsorption of toxins, noxiants and odors,for example from gas or to be more precise air streams. Thehigh-performance adsorbents of the present invention are further usefulfor purifying and cleaning gases, particularly for purifying air, andalso liquids, such as, in particular, water (for example drinking watertreatment). More particularly, the high-performance adsorbents of thepresent invention are useful for impregnation (for example withcatalysts or to be more precise metals or metal salts).

The high-performance adsorbents of the present invention are also usefulfor example for or in the food industry, particularly for preparingand/or decolorizing food products.

The high-performance adsorbents of the present invention can further beused in adsorptive filtering materials or to be more precise in themanufacture of adsorptive filtering materials. Such adsorptive filteringmaterials are useful in the manufacture of protective apparel inparticular, for example protective suits, protective gloves, protectiveunderwear, protective footwear, etc., in particular for the civilian ormilitary sector (for example NBC protection).

The high-performance adsorbents of the present invention are furtheruseful in the sector of medicine or pharmacy, particularly as amedicament or medicament constituent.

The high-performance adsorbents of the present invention can finallyalso be used as sorptive storage media for gases and liquids.

Owing to their high total porosity coupled with high meso- andmacroporosity and similarly a certain degree of microporosity and alsoexcellent mechanical stability with excellent adsorptive properties, thehigh-performance adsorbents of the present invention are distinctlysuperior to comparable adsorbents of the prior art.

Further embodiments, modifications and variations of the presentinvention are readily discernible and realizable for those skilled inthe art on reading the description without their having to leave therealm of the present invention. While the invention has been illustratedand described in detail in the drawings and foregoing description, thesame is to be considered as illustrative and not restrictive incharacter, it being understood that only the preferred embodiment hasbeen shown and described and that all changes and modification that comewithin the spirit of the invention are desired to be protected.

1. High-performance adsorbents based on activated carbon in the form ofdiscrete grains of activated carbon, preferably in spherical form,characterized in that at least 55% of the total pore volume of thehigh-performance adsorbents are formed by pores having pore diameters ofmore than 20 Å, the high-performance adsorbents have a measure ofcentral tendency pore diameter of more than 25 Å, and thehigh-performance adsorbents have a BET surface area of at least 1250m²/g.
 2. The high-performance adsorbents based on activated carbon asclaimed in claim 1, characterized in that the Gurvich total pore volumeof the high-performance adsorbents is at least 0.8 cm³/g, particularlyat least 1.0 cm³/g, preferably at least 1.2 cm³/g, and/or in that theGurvich total pore volume of the high-performance adsorbents reachesvalues of up to 2.0 cm³/g, particularly up to 2.5 cm³/g, preferably upto 3.0 cm³/g, more preferably up to 3.5 cm³/g.
 3. The high-performanceadsorbents based on activated carbon as claimed in claim 1 and/or 2,characterized in that the Gurvich total pore volume of thehigh-performance adsorbents is in the range from 0.8 to 3.5 cm³/g,particularly 1.0 to 3.5 cm³/g, preferably 1.2 to 3.2 cm³/g.
 4. Thehigh-performance adsorbents based on activated carbon as claimed in oneor more of the preceding claims, characterized in that the carbon blackmethod pore volume of the high-performance adsorbents which is formed bypores having pore diameters of more than 20 Å is in the range from 0.4to 3.3 cm³/g, particularly 0.8 to 3.2 cm³/g, preferably 1.0 to 3.1cm³/g, more preferably 1.2 to 3.0 cm³/g, most preferably 1.2 to 2.8cm³/g.
 5. The high-performance adsorbents based on activated carbon asclaimed in one or more of the preceding claims, characterized in that atleast 60%, particularly at least 65%, preferably at least 70%, morepreferably at least 75%, most preferably at least 80% of the total porevolume of the high-performance adsorbents is formed by the pore volumeof pores having pore diameters of more than 20 Å.
 6. Thehigh-performance adsorbents based on activated carbon as claimed in oneor more of the preceding claims, characterized in that 55% to 95%,particularly 60% to 95%, preferably 65% to 90%, more preferably 70 to85% of the total pore volume of the high-performance adsorbents isformed by the pore volume of pores having pore diameters of more than 20Å.
 7. The high-performance adsorbents based on activated carbon asclaimed in one or more of the preceding claims, characterized in thatthe measure of central tendency pore diameter of the high-performanceadsorbents is at least 30 Å, particularly at least 35 Å, preferably atleast 40 Å, and/or in that the measure of central tendency pore diameterof the high-performance adsorbents is in the range from 25 to 75 Å,particularly 30 to 75 Å, preferably 35 to 70 Å, more preferably 40 to 65Å.
 8. The high-performance adsorbents based on activated carbon asclaimed in one or more of the preceding claims, characterized in thatthe BET surface area of the high-performance adsorbents is in the rangefrom 1250 m²/g to 2800 m²/g, particularly 1400 to 2500 m²/g, preferably1500 to 2300 m²/g, more preferably 1600 to 2100 m²/g.
 9. Thehigh-performance adsorbents based on activated carbon as claimed in oneor more of the preceding claims, characterized in that the carbon blackmethod pore surface area formed by pores having pore diameters of morethan 20 Å is in the range from 200 to 1000 m²/g, particularly 250 to 950m²/g, preferably 350 to 900 m²/g, more preferably 400 to 850 m²/g. 10.The high-performance adsorbents based on activated carbon as claimed inone or more of the preceding claims, characterized in that the carbonblack method pore surface area formed by pores having pore diameters ofmore than 20 Å comprises up to 30%, particularly up to 40%, preferablyup to 50% of the total pore surface area of the high-performanceadsorbents, and/or in that the carbon black method pore surface areaformed by pores having pore diameters of more than 20 Å comprises 10 to50%, particularly 15 to 45%, preferably 20 to 40% of the total poresurface area of the high-performance adsorbents.
 11. Thehigh-performance adsorbents based on activated carbon as claimed in oneor more of the preceding claims, characterized in that thehigh-performance adsorbents have a butane adsorption of at least 30%,particularly at least 35%, preferably at least 40%, and/or in that thehigh-performance adsorbents have a butane adsorption in the range from30 to 80%, particularly 35 to 75%, preferably 40 to 70%.
 12. Thehigh-performance adsorbents based on activated carbon as claimed in oneor more of the preceding claims, characterized in that thehigh-performance adsorbents have an iodine number of at least 1250 mg/g,particularly at least 1300 mg/g, preferably at least 1350 mg/g, and/orin that the high-performance adsorbents have an iodine number in therange from 1250 to 2100 mg/g, particularly 1300 to 2000 mg/g, preferably1350 to 1900 mg/g.
 13. The high-performance adsorbents based onactivated carbon as claimed in one or more of the preceding claims,characterized in that the high-performance adsorbents have a methyleneblue value of at least 15 ml, particularly at least 17 ml, preferably atleast 19 ml, and/or in that the high-performance adsorbents have amethylene blue value in the range from 15 to 60 ml, particularly 17 to50 ml, preferably 19 to 45 ml.
 14. The high-performance adsorbents basedon activated carbon as claimed in one or more of the preceding claims,characterized in that the high-performance adsorbents have a molassesnumber of at least 300, particularly at least 350, preferably at least400, and/or in that the high-performance adsorbents have a molassesnumber in the range from 300 to 1400, particularly 350 to 1300,preferably 400 to 1250, most preferably 700 to
 1200. 15. Thehigh-performance adsorbents based on activated carbon as claimed in oneor more of the preceding claims, characterized by a compressive orbursting strength per grain of activated carbon, particularly perspherule of activated carbon, of at least 5 newtons, particularly atleast 10 newtons, preferably at least 15 newtons, and/or characterizedby a compressive or bursting strength per grain of activated carbon,particularly per spherule of activated carbon, in the range from 5 to 50newtons, particularly 10 to 45 newtons, preferably 15 to 40 newtons. 16.The high-performance adsorbents based on activated carbon as claimed inone or more of the preceding claims, characterized by an abrasionresistance of at least 75%, particularly at least 80%, preferably atleast 85%, more preferably at least 90%, most preferably at least 95%.17. The high-performance adsorbents based on activated carbon as claimedin one or more of the preceding claims, characterized in that the carbonblack method micropore surface area of the high-performance adsorbentswhich is formed by pores having pore diameters of ≦20 Å is at least 1000m²/g, particularly at least 1100 m²/g, preferably at least 1200 m²/g,and/or in that the carbon black method micropore surface area of thehigh-performance adsorbents which is formed by pores having porediameters of ≦20 Å is in the range from 1000 to 1800 m²/g, particularly1100 to 1600 m²/g, preferably 1200 to 1500 m²/g.
 18. Thehigh-performance adsorbents based on activated carbon as claimed in oneor more of the preceding claims, characterized in that the carbon blackmethod micropore surface area of the high-performance adsorbents whichis formed by pores having pore diameters of 20 Å comprises at least 30%,particularly at least 40%, preferably at least 50% of the total poresurface area of the high-performance adsorbents, and/or in that thecarbon black method micropore surface area of the high-performanceadsorbents which is formed by pores having pore diameters of ≦20 Åcomprises 50 to 90%, particularly 55 to 85%, preferably 60 to 80% of thetotal pore surface area of the high-performance adsorbents.
 19. Thehigh-performance adsorbents based on activated carbon as claimed in oneor more of the preceding claims, characterized in that the weight-basedadsorbed N₂ volume V_(ads(wt)) of the high-performance adsorbents,determined at a partial pressure p/p₀ of 0.25, is at least 300 cm³/g,particularly at least 350 cm³/g, preferably at least 375 cm³/g, and isparticularly in the range from 300 to 800 cm³/g, preferably 350 to 700cm³/g, more preferably 375 to 650 cm³/g, and/or in that the volume-basedadsorbed N₂ volume V_(ads(vol)) of the high-performance adsorbents,determined at a partial pressure p/p₀ of 0.25, is at least 75 cm³/cm³,particularly at least 100 cm³/cm³, and is particularly in the range from75 to 300 cm³/cm³, preferably 80 to 275 cm³/cm³, more preferably 90 to250 cm³/cm³.
 20. The high-performance adsorbents based on activatedcarbon as claimed in one or more of the preceding claims, characterizedin that the weight-based adsorbed N₂ volume V_(ads(wt)) of thehigh-performance adsorbents, determined at a partial pressure p/p₀ of0.995, is at least 400 cm³/g, particularly at least 450 cm³/g, and isparticularly in the range from 400 to 2300 cm³/g, preferably 450 to 2200cm³/g, more preferably 750 to 2100 cm³/g, and/or in that thevolume-based adsorbed N₂ volume V_(ads(vol)) of the high-performanceadsorbents, determined at a partial pressure p/p₀ of 0.995, is at least200 cm³/cm³, particularly at least 250 cm³/cm³, and is particularly inthe range from 200 to 500 cm³/cm³, preferably 250 to 400 cm³/cm³, morepreferably 275 to 380 cm³/cm³.
 21. The high-performance adsorbents basedon activated carbon as claimed in one or more of the preceding claims,characterized in that the high-performance adsorbents or to be moreprecise the grains of activated carbon, particularly spherules ofactivated carbon, have measure of central tendency particle diameters inthe range from 0.01 to 2.0 mm, particularly 0.01 to 1.0 mm, preferably0.05 to 0.9 mm, more preferably 0.1 to 0.8 mm, most preferably 0.15 to0.7 mm.
 22. The high-performance adsorbents based on activated carbon asclaimed in one or more of the preceding claims, characterized by an ashcontent of at most 1%, particularly at most 0.8%, preferably at most0.6%, more preferably at most 0.5%, and/or characterized by a moisturecontent of at most 1%, particularly at most 0.5%, preferably at most0.2%.
 23. The high-performance adsorbents based on activated carbon asclaimed in one or more of the preceding claims, characterized by a bulkdensity in the range from 150 to 750 g/l, particularly 175 to 650 g/l,preferably 200 to 600 g/l.
 24. The high-performance adsorbents based onactivated carbon in the form of discrete grains of activated carbon,preferably in spherical form, particularly as claimed in one or more ofthe preceding claims, characterized by the following parameters: a porevolume fraction formed by pores having pore diameters of more than 20 Åwhich comprises at least 55% of the total pore volume of thehigh-performance adsorbents, a measure of central tendency pore diameterof more than 25 Å. a BET surface area of at least 1250 m²/g, a methyleneblue value of at least 15 ml, and a molasses number of at least
 300. 25.The high-performance adsorbents based on activated carbon, particularlyas claimed in one or more of the preceding claims, characterized in thatthe high-performance adsorbents are obtainable by a process as claimedin claims 26 to
 34. 26. A process for producing the high-performanceadsorbents based on activated carbon, as claimed in one or more of thepreceding claims, which process comprises a carbonaceous startingmaterial being initially carbonized and subsequently activated,characterized in that the activation is carried out in two stageswherein the carbonized starting material is initially subjected, in afirst activating step, to an activation in an atmosphere comprisingwater vapor, followed by a second activating step of activation in anatmosphere comprising CO₂.
 27. The process as claimed in claim 26,characterized in that the first activating step is carried out attemperatures of 700 to 1300° C., particularly 800 to 1200° C.,preferably 850 to 950° C., and/or for a duration of 5 to 24 hours,preferably 6 to 15 hours, particularly 6 to 12 hours.
 28. The process asclaimed in claim 26 and/or 27, characterized in that the secondactivating step is carried out at temperatures of 700 to 1300° C.,particularly 800 to 1200° C., preferably 850 to 950° C., and/or for aduration of 1 to 10 hours, particularly 3 to 8 hours.
 29. The process asclaimed in one or more of the preceding claims, characterized in thatthe atmosphere of the first activating step comprises or consists ofwater vapor, particularly a mixture of water vapor/inert gas, preferablya mixture of water vapor/nitrogen, particularly where the throughput ofwater vapor is 25 to 350 m³/h, particularly 50 to 300 m³/h, based onpure water vapor, and/or particularly where the mass-based throughput ofwater vapor is 0.01 to 50 l/(h·kg), particularly 0.02 to 25 l/(h·kg),preferably 0.02 to 5 l/(h·kg), reckoned as water and based on the amountof starting material to be activated with water vapor.
 30. The processas claimed in one or more of the preceding claims, characterized in thatthe atmosphere of the second activating step comprises or consists ofCO₂, particularly of pure CO₂ or a mixture of CO₂/inert gas,particularly a mixture of CO₂/nitrogen, particularly where thethroughput of CO₂ is 10 to 250 m³/h, particularly 20 to 200 m³/h, basedon pure CO₂, and/or where the mass-based throughput of CO₂ is 0.001 to100 m³/(h·kg), particularly 0.01 to 50 m³/(h·kg), preferably 0.05 to 10m³/(h·kg), reckoned as pure gaseous CO₂ under activating conditions andbased on the amount of starting material to be activated with CO₂. 31.The process as claimed in one or more of the preceding claims,characterized in that the first and second activating steps merge intoeach other.
 32. The process as claimed in one or more of the precedingclaims, characterized in that the first activating step is carried on toattainment of a predetermined iodine number, particularly to attainmentof an iodine number of at least 1000 mg/g, particularly at least 1250mg/g.
 33. The process as claimed in one or more of the preceding claims,characterized in that the carbonization is carried out at temperaturesin the range from 100 to 950° C., particularly 150 to 900° C.,preferably 300 to 850° C., and/or for a duration of 0.5 to 6 hoursand/or under an inert or at most slightly oxidizing atmosphere.
 34. Theprocess as claimed in one or more of the preceding claims, characterizedin that the carbonaceous starting material comprises sulfonatedstyrene-divinylbenzene copolymers, particularly sulfonateddivinylbenzene-crosslinked polystyrenes, particularly in grain form,preferably in spherical form, particularly where the divinylbenzenecontent of the sulfonated styrene-divinylbenzene copolymers is in therange from 1% to 20% by weight, particularly 1% to 15% by weight,preferably 2% to 10% by weight, based on the styrene-divinylbenzenecopolymers.
 35. The use of the high-performance adsorbents based onactivated carbon as claimed in one or more of the preceding claims forthe food industry, particularly for preparing and/or decolorizing foodproducts.
 36. The use of the high-performance adsorbents based onactivated carbon as claimed in one or more of the preceding claims forthe adsorption of toxins, noxiants and odors, particularly from gas orair streams, or for purifying or cleaning gases, particularly air orliquids, particularly water.
 37. The use of the high-performanceadsorbents based on activated carbon as claimed in one or more of thepreceding claims for use in adsorptive filtering materials, particularlyin the manufacture of protective apparel.
 38. The use of thehigh-performance adsorbents as claimed in one or more of the precedingclaims as sorptive storage media for gases or liquids.
 39. The use ofthe high-performance adsorbents based on activated carbon as claimed inone or more of the preceding claims in the sector of medicine orpharmacy, particularly as a medicament or medicament constituent.